Preparation of nanostructured thin catalytic layer-based electrode ink

ABSTRACT

A method of making an electrode ink containing nanostructured catalyst elements is described. The method comprises providing an electrocatalyst decal comprising a carrying substrate having a nanostructured thin catalytic layer thereon, the nanostructure thin catalytic layer comprising nanostructured catalyst elements; providing a transfer substrate with an adhesive thereon; transferring the nanostructured thin catalytic layer from the carrying substrate to the transfer substrate; removing the nanostructured catalyst elements from the transfer substrate; providing an electrode ink solvent; and dispersing the nanostructured catalyst elements in the electrode ink solvent. Electrode inks, coated substrates, and membrane electrode assemblies made from the method are also described.

STATEMENT OF RELATED CASES

This application is a Continuation-In-Part of U.S. application Ser. No.12/465,913 filed May 14, 2009, entitled ELECTRODE CONTAININGNANOSTRUCTURED THIN CATALYTIC LAYERS AND METHOD OF MAKING, which isincorporated herein by reference.

This application is related to U.S. application Ser. No. 12,718,306,filed Mar. 5, 2010, entitled FABRICATION OF CATALYST COATED DIFFUSIONMEDIA LAYERS CONTAINING NANOSTRUCTURED THIN CATALYTIC LAYERS; and U.S.application Ser. No. 12/718,330, filed Mar. 5, 2010, entitledFABRICATION OF ELECTRODES WITH MULTIPLE NANOSTRUCTURED THIN CATALYTICLAYERS, which are incorporated herein by reference.

FIELD OF THE INVENTION

The present invention relates generally to electrodes for fuel cells,and specifically to nanostructured thin catalytic layer-based electrodeink, and to methods of making such electrode inks.

BACKGROUND OF THE INVENTION

Electrochemical conversion cells, commonly referred to as fuel cells,produce electrical energy by processing reactants, for example, throughthe oxidation and reduction of hydrogen and oxygen. A typical polymerelectrolyte fuel cell comprises a polymer membrane (e.g., a protonexchange membrane (PEM)) with catalyst layers on both sides. Thecatalyst coated PEM is positioned between a pair of gas diffusion medialayers, and a cathode plate and an anode plate are placed outside thegas diffusion media layers. The components are compressed to form thefuel cell.

The currently widely used fuel cell electrocatalysts are platinumnanoparticles supported on carbon supports. Depending on the catalystsand loading, the electrodes prepared with carbon supported platinumcatalysts normally have thickness from several microns to about 10 or 20microns with porosities varying from 30% to 80%. One of thedisadvantages of these carbon supported catalysts is the poor corrosionresistance of carbon under certain fuel cell operating conditions, whichresults in fast performance degradation.

The catalyst layers can be made of nanostructured thin supportmaterials. The nanostructured thin support materials have particles orthin films of catalyst on them. The nanostructure thin catalytic layerscan be made using well known methods. One example of a method for makingnanostructured thin catalytic layers is described in U.S. Pat. Nos.4,812,352, 4,940,854, 5,039,561, 5,175,030, 5,238,729, 5,336,558,5,338,430, 5,674,592, 5,879,827, 5,879,828, 6,482,763, 6,770,337, and7,419,741, and U.S. Publication Nos. 2007/0059452, 2007/0059573,2007/0082256, 2007/0082814, 2008/0020261, 2008/0020923, 2008/0143061,and 2008/0145712, which are incorporated herein by reference. The basicprocess involves depositing a material on a substrate, such aspolyimide, and annealing the deposited material to form a layer ofnanostructured support elements, known as whiskers. One example of amaterial which can be used to form the nanostructured support elementsis “perylene red” (N,N′-di(3,5-xylyl)perylene-3,4,9,10bis(dicarboximide) (commercially available under the trade designation“C. I. PIGMENT RED 149” from American Hoechst Corp. of Somerset, N.J.)).A catalyst material is then deposited on the surface of nanostructuredsupport elements to form a nanostructured thin film (NSTF) catalystlayer, which is available from 3M.

The nanostructured thin catalytic layers can be transferred directly toa proton exchange membrane, such as a DuPont Nafion® membrane, using ahot press lamination process, for example. The polyimide substrate isthen peeled off, leaving the layer of whiskers attached to the membrane.

These types of nanostructured thin catalytic layers have demonstratedhigh catalytic activity, which is helpful to reduce the platinumutilization in fuel cell stacks. Most importantly, because thesupporting layer is not made of carbon as in the traditional platinumcatalysts for fuel cell application, the nanostructured thin catalyticlayers are more resistant to corrosion under certain fuel cell operatingconditions, and thus improve the fuel cell's durability.

However, after the annealing process is completed, a thin layer ofresidual non-crystallized perylene red remains at the surface of thepolyimide substrate. Therefore, when the whiskers have been transferredto the PEM and the polyimide substrate peeled off, the surface of thewhiskers that was adjacent to the polyimide substrate is exposed andbecomes the surface of membrane electrode assembly (MEA). Consequently,the residual non-crystallized perylene red backing, which originally wasadjacent to the polyimide substrate, is exposed. This can be detrimentalto the fuel cell operation because it can block water and gas transferin and out of the electrode.

In addition, an MEA made with this type of whisker catalyst layer has anarrow range of operating conditions (i.e., it cannot be too dry or toowet) to provide good performance. If the fuel cell is operated under wetconditions, the thin layer of whiskers, which is less than 1 μm thick,cannot provide enough storage capacity for the product water, resultingin flooding. Under dry conditions, it is believed that not all portionsof the whiskers are utilized to catalyze the reaction due to poor protontransfer characteristics.

Besides the NSTF whisker catalyst described above, there are otheruniformly dispersed (or dispersed with a desired pattern) catalyticnanostructured materials prepared on a substrate. For example, alignedcarbon nanotubes, aligned carbon nanofibers, or nanoparticles, and thelike could be grown on silicon or other substrates. Catalytic materialsare then deposited onto the nanostructured materials. Electrocatalystdecals incorporating such materials are described, for example, inHatanaka et al., PEFC Electrodes Based on Vertically Oriented CarbonNanotubes, 210^(th) ECS Meeting, Abstract #549 (2006); Sun et al.,Ultrafine Platinum Nanoparticles Uniformly Dispersed on Arrayed CN_(x)Nanotubes with High Electrochemical Activity, Chem. Mater. 2005, 17,3749-3753; Warren et al., Ordered Mesoporous Materials from MetalNanoparticle-Block Copolymer Self-Assembly, Science Vol. 320, 1748-1752(27 Jun. 2008).

Therefore, there is a need for processing and constructing an electrodecontaining catalyst materials which can provide good performance.

SUMMARY OF THE INVENTION

This invention provides a method of harvesting a nanostructured thincatalyst from its carrying substrate and incorporating it into an inkfor further electrode fabrication. Nanostructured thin catalytic layersare transferred from a carrying substrate to a transfer substrate coatedwith an adhesive. The nanostructured catalyst elements are removed fromthe transfer substrate by dissolving the adhesive and dispersed in theelectrode ink. The electrode ink can be coated onto a substrateincluding, but not limited to, an electrode decal, a proton exchangemembrane, or diffusion media. These coated structures can then be usedin MEAs.

One aspect involves a method of making an electrode ink containingnanostructured catalyst elements. The method comprises providing anelectrocatalyst decal comprising a carrying substrate having ananostructured thin catalytic layer thereon, the nanostructure thincatalytic layer comprising nanostructured catalyst elements; providing atransfer substrate with an adhesive thereon; transferring thenanostructured thin catalytic layer from the carrying substrate to thetransfer substrate; removing the nanostructured catalyst elements fromthe transfer substrate; providing an electrode ink solvent; anddispersing the nanostructured catalyst elements in the electrode inksolvent.

Another aspect involves an electrode ink and methods to dispersenanostructured catalyst elements in the electrode ink. The electrode inkcomprises a solvent, and nanostructured catalyst elements and optionallyother particles dispersed in the electrode ink solvent, thenanostructured catalyst elements obtained from a nanotstructured thincatalytic layer transferred from a carrying substrate to a transfersubstrate.

Another aspect involves a coated substrate. The coated substratecomprises a substrate selected from an electrode decal, a protonexchange membrane, or a diffusion media; an electrode ink coated on thesubstrate, the electrode ink comprising nanostructured catalyst elementsdispersed in an electrode ink solvent, the nanostructured catalystelements obtained from a nanostructured thin catalytic layer transferredfrom a carrying substrate to a transfer substrate, and optionally, atleast one additional material selected from ionomer; conductiveparticles, such as carbon powder, carbon fibers; catalyst; titaniumdioxide; silica; nanofibers; or nanotubes.

Another aspect relates to a membrane electrode assembly. The membraneelectrode assembly comprises: a proton exchange membrane having firstand second sides; a pair of gas diffusion media on opposite sides of theproton exchange membrane, the gas diffusion media having first andsecond sides, the first side facing the proton exchange member; and apair of electrode layers between the proton exchange membrane and thepair of gas diffusion media, at least one of the electrode layers formedby coating an electrode ink on the proton exchange membrane, or thefirst side of the pair of gas diffusion media, the electrode inkcomprising nanostructured catalyst elements dispersed in an electrodeink solvent, the nanostructured catalyst elements obtained from ananostructured thin catalytic layer transferred from a carryingsubstrate to a transfer substrate, and optionally, at least oneadditional material selected from ionomer; conductive particles, such ascarbon powder, carbon fibers; catalyst; titanium dioxide; silica;nanofibers; or nanotubes.

Other features and advantages of the present invention will be apparentin light of the description of the invention embodied herein.

BRIEF DESCRIPTION OF THE DRAWINGS

The following detailed description of specific embodiments of thepresent invention can be best understood when read in conjunction withthe following drawings, where like structure is indicated with likereference numerals, where various components of the drawings are notnecessarily illustrated to scale, and in which:

FIGS. 1A-D are an illustration of a general method of transferring ananostructured thin catalytic layer electrode decal from a carryingsubstrate to a transfer substrate.

FIGS. 2A-B are SEM cross-section images of the transferrednanostructured thin catalytic layer on a porous transfer substrate ofFIG. 1C.

FIGS. 3A-B are SEM cross-section images of the transferrednanostructured thin catalytic layer on a nonporous transfer substrate ofFIG. 1C.

FIG. 4A is a micrograph of NSTF nanostructured catalyst elements afterremoval from the transfer substrate, and FIG. 4B is a graph showing theparticle size distribution for the nanostructured catalyst elements.

FIG. 5A is a micrograph of NSTF nanostructured catalyst elements afterultrasonication for 1 min, and FIG. 5B is a graph showing the particlesize distribution for the nanostructured catalyst elements afterultrasonication for 1 min.

FIG. 6A is a micrograph of NSTF nanostructured catalyst elements afterultrasonication for 5 min, and FIG. 6B is a graph showing the particlesize distribution for the nanostructured catalyst elements afterultrasonication for 5 min.

FIGS. 7A-B are SEM cross-section images of a MEA showing the protonexchange membrane and adjacent electrode prepared with an electrode inkcontaining nanostructured catalyst elements.

FIG. 8 is a graph showing the fuel cell performance of a membraneelectrode assembly with nanostructured catalyst elements in theelectrode as shown in FIG. 7.

DETAILED DESCRIPTION

This invention provides a method for making an electrode ink containingnanostructured catalyst elements from nanostructured thin catalyticlayers.

The nanostructured thin catalytic layers are transferred from a carryingsubstrate to a transfer substrate. They are removed from the transfersubstrate and then dispersed into an electrode ink.

The nanostructured catalyst elements can be cleaned either before orafter removal from the transfer substrate. Cleaning can involve removingthe adhesive and/or residual layer with appropriate solvents, or bycentrifuging and sonicating the catalyst elements, filtration or dryingand redispersing.

Additional materials can be incorporated into the electrode ink asdesired (e.g., to increase the water storage capacity, to improve fuelcell performance under dry or wet conditions, or to increaseconductivity). The nanostructured catalyst elements can be dispersedseparately before adding into electrode ink or dispersed simultaneouslywith other materials in the electrode ink.

The nanostructured thin catalytic layer is transferred from the carryingsubstrate to a transfer substrate coated with an adhesive. The transfersubstrate can be porous or non-porous, as desired.

If the transfer substrate is porous, the nanostructured thin catalyticlayer can then be further processed on the porous transfer substrate, ifdesired. The adhesive can be removed, and any residual material (e.g.,non-crystallized perylene red used to make whiskers, or catalysts usedto make carbon nanotubes, and the like) can also be removed. Theseprocesses are described in U.S. application Ser. No. 12/465,913 filedMay 14, 2009, entitled Electrode Containing Nanostructured ThinCatalytic Layers And Method Of Making; U.S. application Ser. No.12/718,306, filed Mar. 5, 2010, entitled Fabrication Of Catalyst CoatedDiffusion Media Layers Containing Nanostructured Thin Catalytic Layers;and U.S. application Ser. No. 12/718,330, filed Mar. 5, 2010, entitledFabrication Of Electrodes With Multiple Nanostructured Thin CatalyticLayers, each of which is incorporated herein by reference.Alternatively, the nanostructured catalyst elements can be removed fromthe transfer substrate first and then further processed, if desired.

If a nonporous transfer substrate is used, the nanostructured catalystelements can be removed from the transfer substrate and then furtherprocessed to remove the adhesive and/or residual layer.

The nanostructured catalyst elements are then dispersed in the electrodeink. There are several ways to disperse the nanostructured catalystelements. One approach would be to separate nanostructured catalystelements from the transfer substrate by dissolving the adhesive,followed by cleaning the catalyst elements by one or more ofcentrifuging, filtration, sonication, drying and redispersing, etc.After the cleansing step, the nanostructured catalyst elements would bedispersed in the electrode ink solvent, along with the various optionalink components, including, but not limited to, ionomer, carbon and otherparticles, and blended together using techniques such as ball milling,media milling, stirring, planetary milling, etc. Suitable electrode inksolvents include, but are not limited to, water, isopropyl alcohol(IPA), ethanol, water/IPA, water/ethanol, and the like. The electrodeink would then be coated on the PEM or gas diffusion media to form theelectrode assembly.

Another approach would be to predisperse the nanostructured catalystelements in a solvent using one of the methods discussed above. Suitablesolvents are listed above. The other components, such as the carbon orconventional Pt/C catalyst powder, would also be separately predispersedin an electrode solvent, which could be the same as that for thenanostructured catalyst elements or different. The two dispersions wouldthen be blended together to form the electrode ink. The advantage ofthis method is that different dispersing methods can be used for the twoinks, and each ink can be controlled and characterized separately interms of solvent selection, ink rheology, and particle size distributionbefore they are blended together to form the final ink. This can yieldpotential improvement in electrode coating quality and improveperformance and durability of the final electrode.

An electrode ink typically contains ionomer, organic solvents such asisopropyl alcohol, ethanol, etc. and electrocatalyst. The variousingredients are combined in predefined concentrations or predispersedseparately as discussed above and subsequently milled/blended togetherusing tools such as ball milling, sonication, etc.

Additional materials can be incorporated into the electrode ink toincrease the electrode performance robustness. Ionic conductingcomponents can be incorporated into the electrode ink, if desired.Hydrophobic particles, for example, PTFE, can be incorporated into theelectrode ink to improve the electrode water management capability, ifdesired. Graphitized or amorphous carbon powder or fiber, other durableparticles, or other electrocatalysts like Pt supported on carbon canalso be incorporated into the electrode ink to increase the electrodewater storage capacity, if desired. An electrode prepared with such anelectrode ink provides good performance over a wider range of operatingconditions, and takes advantage of nanostructured catalyst elements'high catalytic activity and resistance to corrosion under certain fuelcell operating conditions

The nanostructured thin catalytic layer is transferred from the carryingsubstrate to a transfer substrate. The carrying substrate can be thesubstrate the nanostructured thin catalytic layer was grown on orcarried on. The transfer substrate that the nanostructured thincatalytic layer will be transferred to is pre-coated with a thin layerof temporary adhesive. In doing so, the catalyst loading (mg/cm²) on thetransfer substrate is essentially the same as the carrying substratewhere the nanostructured thin catalytic layer was formed.

Because of the transfer of the nanostructured thin catalytic layer fromthe carrying substrate to the transfer substrate, the nanostructuredthin catalytic layer is inverted on the transfer substrate compared tothe carrying substrate. In other words, after the transfer, the surfaceof the nanostructured thin catalytic layer that was exposed on thecarrying substrate is adjacent to the transfer substrate, while thesurface that was adjacent to the carrying substrate is exposed. Thesurface that was adjacent to the carrying substrate can contain residualmaterials that were used to form the nanostructured catalyst elements(e.g., residual non-crystallized perylene red, or catalysts that wereused to grow carbon nanofibers or carbon nanotubes, and the like), whichcan be cleaned through later treatment.

By adjacent, we mean next to, but not necessarily directly next to.There can be one or more intervening layers, as discussed below.

The residual layer is typically the left over materials used to form thenanostructured catalyst support elements. For example, when thenanostructured thin catalytic layer is a layer of whiskers made fromperylene red, the residual layer is non-crystallized perylene red. Forother nanostructured thin catalytic layers, the residual layer would bedifferent. For example, it might be Fe or Ni catalysts used to growcarbon nanofibers or carbon nanotubes.

To simplify the discussion in the following illustrations, ananostructured thin catalytic layer made from perylene red on apolyimide carrying substrate was chosen as a specific example. But inthe case of other material sets, the carrying substrate would bedifferent from the polyimide (e.g., silicon), and the nanostructuredsupport elements could be different from the perylene red (e.g., carbonnanotubes).

FIGS. 1A-D illustrate the general steps involved in transferring ananostructured thin catalytic layer from a carrying substrate to atransfer substrate. FIG. 1A shows a transfer substrate 105 coated withan adhesive layer 110. The transfer substrate 105 can be any stiff orsoft substrate. If the nanostructured thin catalytic layer is made on asmooth substrate, a stiffer substrate can be used as the transfersubstrate. Stiff substrates can also be used if a thick layer of thetemporary adhesive is coated on the transfer substrate, and thethickness of the adhesive layer is thicker than the roughness feature(e.g., corrugations) of the carrying substrate. For example, if thecarrying substrate has a surface feature (e.g., corrugations) which is 6microns between the highest and lowest points of the corrugatedstructure, then the thickness of the adhesive layer should be greaterthan 6 microns.

The transfer substrate can be porous or non-porous.

If a porous transfer substrate is used, the pores act as a drain forwaste products used in further cleaning the nanostructured thincatalytic layer while keeping the nanostructured thin catalytic layer onthe porous substrate. Soft porous substrates can accommodate the surfaceroughness of the carrying substrate if the nanostructured thin catalyticlayers were not made on smooth substrates. Suitable types of poroussubstrates include, but not limited to, porous polyethylene (PE), porouspolypropylene (PP), porous polyester, porous Nylon, porous polyimide(PI), expanded polytetrafluoroethylene (ePTFE), and porous siloxane.

One suitable porous substrate is expanded polytetrafluoroethylene(ePTFE). ePTFE is soft which allows it to receive the nanostructuredthin catalytic layers from both the top and the bottom of thecorrugations of the electrocatalyst decal on which they were grown.ePTFE has another advantage when an adhesive dissolved in a hydrophilicsolution is used. Because ePTFE is hydrophobic, only a thin film of theadhesive, such as polyvinyl alcohol (PVA), is formed on the surface ofthe ePTFE when the adhesive is coated from a PVA water solution, and thePVA will not fill the pores of the ePTFE substrate.

Nonporous substrates can also be used. In this case, the nanostructuredthin catalyst layer will typically be removed from the transfersubstrate before further cleaning. Depending on the particularnanostructured material, an inexpensive, readily available commoditypolymer can be used as the transfer substrate, which will make theprocess very cost-effective during high volume manufacturing. Examplesof suitable nonporous substrates include, but are not limited to, PET,PEN, PP, PE, PS and PC.

The transfer substrate can be reused, if desired, making the processmore cost effective.

The temporary adhesive layer 110 adheres the nanostructured thincatalytic layer and the transfer substrate together, allowing theremoval of the nanostructured thin catalytic layer from its carryingsubstrate. Any suitable adhesive can be used. Desirably, the adhesive iseasily removable, and does not poison the catalyst. Water solubleadhesives are desirable because they can be easily removed with waterand water is the reaction product during fuel cell operations. However,other solvents can be used to remove the adhesive, if desired. Suitableadhesives include, but are not limited to, polyvinyl alcohol (PVA),polyethylene oxide, polyacrylate, polyethylene vinyl acetate, andsoluble cellulose. One suitable adhesive is a water soluble PVA, forexample, a water soluble PVA having a molecular weight (MW) of about10,000. Generally, the PVA layer loading is between about 0.1 mg/cm² andabout 10 mg/cm², or about 0.5 mg/cm² to about 2 mg/cm².

The transfer substrate can be either hydrophobic or hydrophilic.Preferably, an adhesive soluble in an aqueous or hydrophilic solution isapplied when the porous transfer substrate is hydrophobic, or viceversa. This allows a thin film of the adhesive to form only on thesurface of the porous transfer substrate. In this way, the pores are notfilled with the adhesive initially.

As shown in FIG. 1B, an electrocatalyst decal is provided. Theelectrocatalyst decal includes a carrying substrate 115 withnanostructured thin catalytic layer 125 on it. In some cases, there maybe a residual layer 120 of the material used to form the nanostructurednanostructured catalyst elements between the carrying substrate 115 andthe nanostructured thin catalytic layer 125. The nanostructured thincatalytic layer has a first surface 122 adjacent to the carryingsubstrate and an exposed second surface 128.

Suitable electrocatalyst decals comprising whiskers made from perylenered on a polyimide substrate known as NSTF catalyst layers are availablefrom 3M. Other electrocatalyst decals with nanostructured thin catalyticlayers could also be used. The nanostructured catalytic materials areeither uniformly dispersed on the substrate or dispersed in a desiredpattern. For example, aligned carbon nanotubes, aligned carbonnanofibers, or nanoparticles, and the like with uniformly dispersedcatalyst could be used. Electrocatalyst decals incorporating suchmaterials are described, for example, in Hatanaka et al., PEFCElectrodes Based on Vertically Oriented Carbon Nanotubes, 210^(th) ECSMeeting, Abstract #549 (2006); Sun et al., Ultrafine PlatinumNanoparticles Uniformly Dispersed on Arrayed CN_(x) Nanotubes with HighElectrochemical Activity, Chem. Mater. 2005, 17, 3749-3753; Warren etal., Ordered Mesoporous Materials from Metal Nanoparticle-BlockCopolymer Self-Assembly, Science Vol. 320, 1748-1752 (27 Jun. 2008).

The nanostructured thin catalytic layer on the carrying substrate isinverted, and the second surface 128 of the nanostructured thincatalytic layer 125 is placed in contact with the adhesive layer 110 toform a composite structure. Suitable processes include, but are notlimited to, static pressing with heat and pressure, or for continuousroll production, laminating, nip rolling, or calendering. The carryingsubstrate 115 is then removed (for example, by peeling off the carryingsubstrate). As shown in FIG. 1C, after the carrying substrate isremoved, the residual layer 120 (if present) remains on thenanostructured catalytic layer 125.

When a porous transfer substrate is used, the adhesive layer 110 can bethen removed by a suitable process, as shown in FIG. 1D. One example ofa suitable process involves rinsing the composite structure with asolvent to dissolve the adhesive. The solvent desirably wets the surfaceof the porous transfer substrate 105. Suitable solvents include, but arenot limited to, water/alcohol mixtures, such as for example, awater/isopropanol (IPA) mixture when an ePTFE substrate is used. Thealcohol in the water/alcohol mixture helps wet the hydrophobic ePTFEsubstrate, and the pores of the porous substrate act as a drain for thesolvent.

The nanostructured thin catalytic layer 125 can be further treated toremove the residual layer 120 (if necessary), exposing the first surface122 of the nanostructured thin catalytic layer 125. The residual layer120 can be removed by any suitable process. One example of a suitableprocess is rinsing the nanostructured thin catalytic layer with asolvent to remove the residual layer. If the nanostructured thincatalytic layer comprises whiskers made from perylene red, suitablesolvents for perylene red, include, but are not limited to, mixtures ofwater, acetone, n-propanol (NPA), or 1-methyl-2-pyrolidone (NMP).Water/NPA mixtures can dissolve small amounts of perylene red (lowsolubility). NMP appears to be very effective to dissolve perylene red,but it has a high boiling point and thus further solvent rinsing isrequired to fully remove it. Consequently, mixtures of the abovementioned solvents are preferred to perform the cleaning process. Again,the pores of the porous substrate act as a drain for the solvent anddissolved residual materials. If Fe or Ni catalysts are used to growcarbon nanotubes or carbon nanofibers, nitric acid, sulfuric acid, andother acids could be used to dissolve the residual metals. Alcohol couldbe added to the acidic solution to help wet the ePTFE substrate, ifdesired.

The adhesive layer 110 and residual layer 120 can be removedsimultaneously by applying solvents for both layers at the same time.Alternatively, one layer can be removed after the other. In thissituation, the adhesive layer 110 would preferably be removed first inorder to clear up the path to the pores in the porous transfersubstrate.

As shown in FIG. 1D, a vacuum 130 can be applied during the removal ofthe adhesive layer, and/or the removal of the residual layer, ifdesired.

If a nonporous transfer substrate is used, the nanostructured thincatalytic layer can be removed from the transfer substrate by dissolvingthe adhesive on the transfer substrate with a proper solvent. Theresidual layer can be removed later during the cleaning step. Thenanostructured catalyst elements can be cleaned to remove the temporaryadhesive by centrifuging, filtration, sonication, drying andredispersing, or combinations thereof with appropriate solvents.

Once the nanostructured catalyst elements have been cleaned, they aredispersed in an electrode ink, further containing ink solvent, ionomer,carbon and other particles, blended together using techniques such asball milling, media milling, stirring, planetary milling andsubsequently coated to form the electrode. Another approach would be todisperse only the nanostructured catalyst elements in a solvent usingone of the methods discussed above, and in a separate step, predispersecarbon or Pt/C catalyst powder in the electrode solvent (and any othercomponents) before the nanostructured catalyst elements are added. Theadvantage of this method is that different dispersing methods can beused for the two dispersions. The dispersions can be controlled andcharacterized separately in terms of solvent selection, ink rheology,and particle size distribution before they are blended together to formthe final ink. This can yield potential improvement in coating quality,performance and durability of the final electrode.

The electrode ink can include one or more of ionomer; conductiveparticles, including but not limited to, carbon powder, and carbonfiber; catalyst; titanium dioxide; silica; nanofibers; nanotubes; orcombinations thereof. For example, an ionomer can be added to increasethe proton conduction of the catalyst under dry conditions. Ahydrophobic component, such as PTFE particles, can be included toimprove wet performance.

Conductive particles, such as carbon (powder, fibers, or both), orcatalyst (typically the catalyst would be on a conventional carbonsupport) can be included to increase the overall electrode thickness andthus improve the product water storage capability.

More durable conductive particles can also be used to provide void spacewithin the electrode for product water storage. Suitable compoundsinclude, but are not limited to, conductive borides, carbides, nitrides,and silicides (B, C, N, Si). Suitable metals for the conductiveparticles include, but are not limited to Co, Cr, Mo, Ni, Ti, W, V, Zr.The use of such compounds, for example, TiN, is described in USPublication 2006/251954. One advantage of nanostructured thin catalyticlayers over carbon supported electrodes is durability enhancementbecause the carbon support is susceptible to corrosion especially duringfuel cell startup. These other conductive materials have not been fullysuitable for electrode supports because they do not provide enoughsurface area, and consequently, Pt dispersion, as is obtainable withcarbon. However, for the present use, the conductive particles wouldonly need to function to provide void space and conductivity but notcatalyst support, so the high surface area is not needed. Materialdurability is needed in the acidic and high electrochemical potentialfuel cell environment. Thus, their use would be acceptable.

Titanium dioxide and/or silica, which are hydrophilic and could be usedto retain product water under dry conditions, can also be included. Theaddition of non-conductive particles such as titanium dioxide or silicawould likely require the addition of a conductive material to providethe electrical conductivity function. Ionomer could also be added tothis layer or be pulled in by later coating processes to provide theneeded protonic conductivity for this layer. Nanofibers and/ornanotubes, which can be used as structural materials to incorporate intothe intermediate layer, can also be used.

The electrode ink containing the nanostructured catalyst elements madeby the above process can then be used in conventional electrode and MEAfabrication methods. For example, the electrode ink can be coated onsubstrates including, but not limited to, electrode decals, protonexchange membranes, and diffusion media.

Example 1

A water soluble PVA (molecular weight around 10,000) adhesive layerthrough a 5 wt % aqueous solution was coated on an ePTFE poroussubstrate. The PVA loading is about 0.6 mg/cm² after drying.

A 3M NSTF catalyst layer (0.15 mg Pt/cm²) supported on a carryingsubstrate was provided. It included a polyimide carrying substrate, anda nanostructured thin catalytic layer of whiskers made from perylenered. There was a residual layer of perylene red on the interface betweenthe whiskers and the polyimide carrying substrate. Using a hot press(105° C., 3.5 MPa, 4 minutes) process, the second surface of the layerof whiskers was pressed against the PVA adhesive layer on the ePTFEporous transfer substrate. The carrying substrate was then peeled off,leaving whisker layer on the porous transfer substrate and the residuallayer of perylene red exposed.

FIGS. 2A-B show SEM images of the 3M NSTF catalyst layer 125 (0.15 mgPt/cm²) transferred to the ePTFE transfer substrate 105 using the PVAadhesive 110.

The NSTF catalyst layer was then cleaned by washing the layer with awater/IPA (1:1 weight ratio) mixture solution multiple times until thesolvent drained freely through the ePTFE substrate. An EtOH/NPA (1:1)mixture solution was then coated on top of the whiskers multiple timesto remove the residual layer of perylene red, exposing first surface.

After the NSTF catalyst layer had been cleaned, the nanostructuredcatalyst elements were rinsed off the ePTFE substrate by washing withwater.

Example 2

A water soluble PVA (molecular weight around 10,000) adhesive layerthrough a 15 wt % aqueous solution was coated on a polyimide nonporoussubstrate The PVA loading is about 1.2 mg/cm² after drying.

A 3M NSTF catalyst layer supported on a carrying substrate was provided.It included a polyimide carrying substrate, and a nanostructured thincatalytic layer of whiskers made from perylene red. There was a residuallayer of perylene red on the interface between the whiskers and thepolyimide carrying substrate. Using a hot press (105° C., 3.5 MPa, 4minutes) process, the second surface of the layer of whiskers waspressed against the PVA adhesive layer on the polyimide nonporoustransfer substrate. The carrying substrate was then peeled off, leavingwhisker layer on the nonporous transfer substrate 105 and the residuallayer of perylene red exposed.

FIGS. 3A-B show SEM images of the 3M NSTF catalyst layer 125 transferredto the polyimide nonporous transfer substrate 105 using the PVA adhesive110.

The nanostructured catalyst elements were removed from the polyimidetransfer substrate by rinsing with a water solution in a sonicationbath. Clean up of the sample was accomplished in a two step process. Inthe first step, the nanostructured elements were vacuum filtered througha submicron sized filter. Subsequently, the nanostructured catalystelements were centrifuged in a graduated centrifuge tube and thesupernatant liquid was decanted. Clean water was then added to the tubewhich was sonicated to redisperse the nanostructured catalyst elements.FIG. 4A is a micrograph of the unsonicated nanostructured catalystelements. FIG. 4B shows the particle size distribution of theunsonicated nanostructured catalyst elements. The NSTF nanostructuredcatalyst elements have mean particle diameter peaks centered around 6 μmand 30 μm.

FIG. 5A is a micrograph of the nanostructured catalyst elements aftersonication for 1 min in water. FIG. 5B shows the particle sizedistribution of the nanostructured catalyst elements sonicated for 1min. The NSTF nanostructured catalyst elements have begun todisintegrate into smaller clumps with mean particle diameter peakscentered around 4 μm and 18 μm.

After sonication for 5 min, more significant disintegration hasoccurred, as shown in FIGS. 6A-B. There are sharper peaks around 4 μmand 18 μm, and a shoulder at around 1.75 μm, which indicates thepresence of smaller particles that can be uniformly dispersed.

Example 3

The nanostructured catalyst elements were removed from the polyimidetransfer substrate by rinsing with a water solution in a sonication bathas described above in Example 2 and dispersed using intense hornsonication at 20 W for 5 min.

An ink composed of Vulcan XC-72 carbon black, and DuPont Nafion® DE 2020ionomer was premixed through ball milling process and was then blendedtogether with the above dispersed nanostructured catalyst elements toprepare the final electrode ink. The weight ratio between thenanostructured catalyst elements and the Vulcan XC-72 carbon black was0.25, and the ionomer to carbon weight ratio was 0.8 in the finalelectrode ink. An electrode decal was prepared by coating the electrodeink on an ETFE substrate using a meyer rod. The carbon black loading was0.28 mg/cm², and the Pt loading was 0.07 mg/cm². After the electrodedecal is dried, it was hot pressed to a DuPont Nafion® NRE211 membrane,and the ETFE decal was peeled off. The resulting MEA was characterizedby SEM and tested for fuel cell performance on a test stand.

FIGS. 7A-B show the SEM cross section of the MEA discuss above. Thenanostructured catalyst elements 160 were dispersed uniformly in theelectrode layer 155. The electrode layer 155 was about 11 μm, which issignificantly thicker that conventional NSTF electrodes (about 0.5 μm).This provides the electrode system with more water buffer capacityduring wet operating conditions and high current density operations.

FIG. 8 shows the fuel cell performance of the above MEA. It is plottedbetween high frequency resistance corrected voltage and hydrogencross-over corrected current using hydrogen/pure oxygen as reactants(stoichiometric ratios of 2 and 9.5 respectively), at 80 C, 50 kPa gaugepressure, 100% RH. High frequency resistance (HFR) represents the fuelcell internal ohmic resistances, predominated by protonic resistance inthe membrane and contact resistances of multiple interfaces. The Ptcatalytic mass activity for this electrode containing redispersednanostructured catalyst elements (the current density at 900 mV dividedby the Pt loading) was estimated to be around 0.07 A/mg Pt. Theelectrochemically specific surface area from hydrogenadsorption/desorption measurement for this electrode was around 9 m²/gPt, and the Pt specific activity was determined to be around 800 μA/cm²Pt. These results are comparable to that of the baseline NSTF catalystshot pressed directly to a PFSA membrane. It indicates that thisredispersed nanostructured catalyst elements electrode maintains thecatalytic activity of the nanostructured thin film catalysts but wouldhave a significantly larger water buffer capacity with the totalelectrode thickness being around 11 microns.

It is noted that terms like “preferably,” “commonly,” and “typically”are not utilized herein to limit the scope of the claimed invention orto imply that certain features are critical, essential, or evenimportant to the structure or function of the claimed invention. Rather,these terms are merely intended to highlight alternative or additionalfeatures that may or may not be utilized in a particular embodiment ofthe present invention.

For the purposes of describing and defining the present invention it isnoted that the term “device” is utilized herein to represent acombination of components and individual components, regardless ofwhether the components are combined with other components. For example,a “device” according to the present invention may comprise anelectrochemical conversion assembly or fuel cell, a vehicleincorporating an electrochemical conversion assembly according to thepresent invention, etc.

For the purposes of describing and defining the present invention it isnoted that the term “substantially” is utilized herein to represent theinherent degree of uncertainty that may be attributed to anyquantitative comparison, value, measurement, or other representation.The term “substantially” is also utilized herein to represent the degreeby which a quantitative representation may vary from a stated referencewithout resulting in a change in the basic function of the subjectmatter at issue.

Having described the invention in detail and by reference to specificembodiments thereof, it will be apparent that modifications andvariations are possible without departing from the scope of theinvention defined in the appended claims. More specifically, althoughsome aspects of the present invention are identified herein as preferredor particularly advantageous, it is contemplated that the presentinvention is not necessarily limited to these preferred aspects of theinvention.

What is claimed is:
 1. A method of making an electrode ink containingnanostructured catalyst elements comprising: providing anelectrocatalyst decal comprising a carrying substrate having ananostructured thin catalytic layer thereon, the nanostructure thincatalytic layer comprising nanostructured catalyst elements; providing atransfer substrate with an adhesive thereon; transferring thenanostructured thin catalytic layer from the carrying substrate to thetransfer substrate; cleaning and dispersing the nanostructured catalystelements; removing the nanostructured catalyst elements from thetransfer substrate; providing an electrode ink solvent; and dispersingthe nanostructured catalyst elements in the electrode ink solvent. 2.The method of claim 1 wherein the nanostructured catalyst elements arecleaned before the nanostructured catalyst elements are removed from thetransfer substrate.
 3. The method of claim 1 wherein the nanostructuredcatalyst elements are cleaned after the nanostructured catalyst elementsare removed from the transfer substrate.
 4. The method of claim 1wherein cleaning the nanostructured catalyst elements comprises washingthe nanostructured catalyst elements with a solvent using filtration,centrifuging, drying and redispersing, or combinations thereof.
 5. Themethod of claim 1 wherein cleaning the nanostructured catalyst elementscomprises sonicating the nanostructured catalyst elements.
 6. The methodof claim 1 wherein the nanostructured catalyst elements are dispersed inthe electrode ink solvent using a process selected from ultrasonicating,ball milling, media milling, mechanical milling, or combinationsthereof.
 7. The method of claim 1 wherein dispersing the nanostructuredcatalyst elements in the electrode ink solvent comprises: predispersingthe nanostructured catalyst elements in a first electrode ink solvent;predispersing at least one additional material selected from ionomer,carbon powder, carbon fibers, or catalyst, titanium dioxide, silica,nanofibers, or nanotubes in a second electrode ink solvent; and blendingthe predispersed nanostructured elements and the predispersed at leastone additional material together to form the electrode ink.
 8. Themethod of claim 7 wherein the nanostructured catalyst elements arepredispersed in the first electrode ink solvent using ultrasonicating,ball milling, media milling, mechanical milling, or combinationsthereof.
 9. The method of claim 7 wherein the at least one additionalmaterial is predispersed in the second electrode ink solvent using ballmilling, media milling, planetary milling, ultrasonication, stirring ora combination thereof.
 10. The method of claim 1 wherein at least oneadditional material selected from ionomer, conductive particles, carbonpowder, carbon fibers, catalyst, titanium dioxide, silica, nanofibers,or nanotubes is dispersed in the electrode ink solvent with thenanostructured catalyst elements.
 11. The method of claim 1 wherein theadhesive layer comprises a water soluble adhesive.
 12. The method ofclaim 1 further comprising coating the electrode ink containing thenanostructured catalyst elements on a substrate selected from a protonexchange membrane, a diffusion media, or an electrode decal.
 13. Themethod of claim 1 wherein transferring the nanostructured thin catalyticlayer from the carrying substrate to the transfer substrate comprises:adhering the nanostructured thin catalytic layer adjacent to theadhesive to form a composite structure; and removing the carryingsubstrate from the composite structure.
 14. The method of claim 13wherein the nanostructured thin catalytic layer is adhered adjacent tothe adhesive using static pressing with heat and pressure, laminating,nip rolling, or calendering, or combinations thereof.